Fuels and lubricants containing aminoguanidine antioxidants

ABSTRACT

Organic compositions are provided containing, as improving agents, compounds selected from the group consisting of ketimines of aminoguanidine, aldimines of ketimines of aminoguanidine and aldimines of amides of aminoguanidine. These compounds act as antioxidants and metal deactivators for fuel oils, lubricating oils and greases.

United States Patent Andress, Jr. [4 1 Apr. 11, 1972 [54] FUELS ANDLUBRICANTS [56] References Cited CONTAINING AMINOGUANIDINE UNITED STATESPATENTS ANTIOXIDANTS 1,972,760 9/1934 Calcott et al ..44/74 X [72]Inventor: Harry Andrew, Pltman, 2,353,690 7/1944 Clarkson et al..252/51.5 A e I M bi] 1C 6 2,584,784 2/1952 Biswell ..252/5l.5 A [73]Assgnee 3,449,424 6/1969 Andress et al. ..252/515 [22] Filed: May 18,1970 Primary Examiner-Patrick P. Garvin [21] Appl' 38500 AssistantExaminer-W. J. Shine Attorney-Oswald G. Hayes, Andrew L. Gaboriault,Raymond [52] US. Cl. ..252/51.5 A, 252/50, 252/5 1.5 R, Barclay andBenjamin L Kaufman 252/403, 260/404.5, 260/558 P, 260/562 P, [57]ABSTRACT 260 564 F 51 1m. Cl ..Cl0m1/32,Cl0m 1/36, Cl( )l 1/22 Organiccompositions are provided containing, as improving [58] Field of Search.,252/50, 51.5 R, 51.5 A, 401, agents, Compounds Selected from the groupconsisting of 252/403; 44/66 71, 7 74 75; 4045 5 53 p ketimines ofaminoguanidine, aldimines of ketimines of 562 p 564 F aminoguanidine andaldimines of amides of aminoguanidine.

These compounds act as antioxidants and metal deactivators for fueloils, lubricating oils and greases.

14 Claims, N0 Drawings FUELS AND LUBRICANTS CONTAINING AMINOGUANIDINEAN'I'IOXIDANTS BACKGROUND OF THE INVENTION 1. Field of the InventionThis invention relates to organic compositions and, in one of itsaspects, relates more particularly to improved organic compositions inthe form of liquid and solid hydrocarbons which, when employed as fueloils, normally cause gum formation upon combustion or, when in the formof lubricating oils or greases, are subject to oxidative deterioration.Still more particularly, in this aspect, the invention relates toimproved organic compositions in the form of petroleum distillatehydrocarbon fuels, lubricating oils or greases which, in theiruninhibited state, tend to result in the above-described deleteriousconditions in the course of use or storage.

2. Description of the Prior Art It is well known that certain types oforganic compositions in the form of liquid hydrocarbon fuels normallyresult in gum formation or cause screen clogging upon combustion.Furthermore, it is also known that organic compositions, when employedin the form of lubricating oils or greases containing such oils asvehicles, are subject to oxidative deterioration in the course of theirfunctional environment, thus clearly indicating the necessity forincorporating into such organic compositions effective improving agents.

SUMMARY OF THE INVENTION It has now been found that the aforementionedgum formation or oxidative deterioration properties of organiccompositions, particularly in the form of fuels and lubricants can beeffectively overcome by incorporating therein small amounts of anadditive agent selected from the group consisting of ketimines ofaminoguanidine, aldimines of ketimines of aminoguanidine and aldiminesof amides of aminoguanidine.

In general, the present invention, in its preferred applications,contemplates organic compositions of the abovedescribed types whichcontain a small amount of the aforementioned aminoguanidine, usuallyfrom about 0.1 to about 200 pounds per thousand barrels, and preferablyfrom about 1 toabout lpounds per thousand barrels of the total weight ofsuch compositions.

The organic compositions improved in accordance with the presentinvention may comprise any materials that are normally susceptible tothe above-described screen clogging or oxidative deteriorationcharacteristics. A field of specific applicability is the improvement ofliquid hydrocarbons boiling from about 75 to about l,000 F. Ofparticular significance is the treatment of petroleum distillate fuelshaving an initial boiling point from about 75 to about 135 F. and an endboiling point from about 250 to about 750 F. It should be noted, in thisrespect, that the term distillate fuels is not intended to be restrictedto straight-run distillate fractions. These distillate fuel oils can bestraight-run distillate fuels, catalytically or thermally cracked(including hydrocracked) distillate fuels, or mixtures of straight-rundistillate fuels, naphthas and the like, with cracked distillate stocks.Moreover, such fuels can be treated in accordance with well-knowncommercial methods, such as acid or caustic treatment, hydrogenation,solventrefining, clay treatment and the like.

The distillate'fuels are characterized by their relatively lowviscosity, pour point and the like. The principal property whichcharacterizes these hydrocarbons, however, is their distillation range.As hereinbefore indicated, this range will lie between about 75 andabout 750 F. Obviously, the distillation range of each individual fuelwill cover a narrower boiling range, falling nevertheless within theabove-specified limits. Likewise, each fuel will boil substantially,continuously throughout its distillation range.

Particularly contemplatedamong the fuels are Numbers 1, 2 and 3fuel oilsused in heating and as diesel fuel oils, gasoline and jet combustionfuels. The domestic fuel oils generally conform to the specificationsset forth in ASTM Specification D396-48T. Specifications for dieselfuels are defined in ASTM Specifications D975-48T. Typical jet fuels aredefined in Military Specification MlL-F-5624B. In addition, aspreviously indicated, hydrocarbon lubricating oils of varying viscosityand pour points, falling both within the aforementioned range and ashigh as l,000 F. and higher may also be effectively treated through theuse of the aforementioned additive agents.

As previously indicated, the aforementioned additive agents of thepresent invention may also be incorporated as antioxidants in greasecompositions. Such greases may comprise a combination of a wide varietyof lubricating vehicles and thickening or gelling agents. Thus greasesin which the aforementioned additive agents are particularly effective,may comprise any of the conventional hydrocarbon oils of lubricatingviscosity, as the oil vehicle, and may include mineral or syntheticlubricating oils, aliphatic phosphates, esters and diesters, silicates,siloxanes and oxalkyl ethers and esters. Mineral lubricating oils,employed as the lubricating vehicle, may be of any suitable lubricatingviscosity range from about 45 SSU at 100 F. to about 6,000 SSU at 100F., and, preferably, from about 50 to about 250 SSU at 210 F. These oilsmay have viscosity indexes varying from below 0 to about 100 or higher.Viscosity indexes from about 70 to about are preferred. The averagemolecular weights of these oils may range from about 250 to about 800.The lubricating oil is employed in the grease composition in an amountsufficient to constitute the balance of the total grease composition,after accounting for the desired quantity of the thickening agent, andother additive components to be included in the grease formulation.

As previously indicated, the oil vehicles employed in the novel greaseformulations of the present invention, in which the aforementionedagents are incorporated as antioxidative agents may comprise mineral orsynthetic oils of lubricating viscosity. When high temperature stabilityis not a requirement of the finished grease, mineral oils having aviscosity of at least 40 SSU at F., and particularly those fallingwithin the range from about 60 SSU to about 6,000 SSU at 100 F., may beemployed. In instances where synthetic vehicles are employed rather thanmineral oils, or in combination therewith, as the lubricating vehicle,various compounds of this type may be successfully utilized. Typicalsynthetic vehicles include: polypropylene, polypropylene glycol,trimethylol propane esters, neopentyl and pentaerythritol esters, di( 2-ethyl hexyl) sebacate, di(2-ethyl hexyl) adipate, di-butyl phthalate,fiuorocarbons, silicate esters, silanes, esters of phosphorus-containingacids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils,chain-type polyphenyls, siloxanes and silicones (polysiloxanes),alkyl-substituted diphenyl ethers typified by a butyl-substitutedbis(p-phenoxy phenyl) ether, phenoxy phenylethers, etc.

The lubricating vehicles of the aforementioned improved greases of thepresent invention containing the abovedescribed additive agents arecombined with a grease-forming quantity of a thickening agent. For thispurpose, a wide variety of materials may be employed. These thickeningor gelling agents may include any of the conventional additive agents orsoaps, which are dispersed in the lubricating vehicle in greaseformingquantities in such degree as to impart to the resulting greasecomposition the desired consistency. Other thickening agents that may beemployed in the grease formulation may comprise the non-soap thickeners,such as surface-modified clays and silicas, aryl ureas, calciumcomplexes and similar materials. In general, grease thickeners may beemployed which do not melt and dissolve when used at the requiredtemperature within a particular environment; however, in all otherrespects, any material which is normally employed for thickening orgelling hydrocarbon fluids for forming grease can be used in preparingthe aforementioned improved grease in accordance with the presentinvention.

The novel improving agents of the present invention may be prepared, ingeneral, by reacting an aminoguanidine salt with a ketone to produce thecorresponding ketimine of aminoguanidine; or a ketimine ofaminoguanidine thus produced may be further reacted with an aldehyde toproduce the corresponding aldimine of the ketimine of aminoguanidine.Each of these reactions can be carried out at a temperature from about100 to about 200 C. and in a mo] ratio of 1:1. It is also within thescope of the invention to react an aminoguanidine salt, an organic acidand an aldehyde, at the above temperature range and in a mol ratio of1:1:1, to produce the corresponding aldimine of the amide ofaminoguanidine. For the above described reactions, a wide variety ofaminoguanidine salts, ketones, aldehydes, acids and derivatives thereofmay be successfully employed.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following data and examples willserve to illustrate the preparation of the novel additive agents of thepresent invention and their efficacy as improving agents in organiccompositions. It will be understood, however, that it is not intendedthe invention be limited to the particular additive agents or theparticular organic compositions containing these agents, as described.Various modifications of these agents and organic compositions can beemployed and will readily be apparent to those skilled in the art.

EXAMPLE 1 Preparation of the Methylcoco Ketimine of Aminoguanidine Amixture of 68 grams (0.5 mol) aminoguanidine bicarbonate, 110 grams (0.5mol) methylcoco ketone and 100 grams of benzene diluent was refluxed toa temperature of about 175 C. over a period of about 8 hours to producethe final product, viz. the methylcoco ketimine of aminoguanidine.

EXAMPLE 2 Preparation of the salicylaldimine of the Methylcoco Ketimineof Aminoguanidine To 159 grams (0.5 mol) of the product prepared inaccordance with Example 1 were added 61 grams (0.5 mol) salicylaldehydeand 100 grams of toluene. The resulting mixture was stirred at atemperature of 175 C. for a period of about 3 hours to produce the finalproduct, viz. the salicylaldimine of the methylcoco ketimine ofaminoguanidine.

EXAMPLE 3 Preparation of the Salicylaldimine of the Methylnonyl Ketimineof Aminoguanidine A mixture of 136 grams (1.0 mol) aminoguanidinebicarbonate, 170 grams (1 mol) methylnonyl ketone and 100 grams ofbenzene as a diluent was refluxed to a temperature of about 180 C. overa period of about 8 hours. The resulting mixture was then cooled to 90C. and 122 grams (1 mol) salicylaldehyde and 200 grams toluene wereadded. The resulting mixture was then refluxed to a temperature of about177 C. over a 6 hour period to produce the final product, viz. thesalicylaldimine of the methylnonyl ketimine of aminoguanidine.

EXAMPLE 4 Preparation of the salicylaldimine of Phenylstearyl Amide ofAminoguanidine A mixture of 68 grams (0.5 mol) aminoguanidinebicarbonate, 100 grams (0.5 mol) phenylstearic acid and 100 gramsbenzene was refluxed to a temperature of about 177 C. over a period ofabout 8 hours. The resulting mixture was cooled to 80 C. and 61 grams(0.5 mol) salicylaldehyde and 100 grams toluene were added. Theresulting mixture was then refluxed to a temperature of about 178 C.over a 6 hour period to produce the final product, viz. thesalicylaldimine of phenylstearyl amide of aminoguanidine.

The novel ketimines of aminoguanidine, as illustrated by Example 1, havethe following general structural formula:

in which R, and R are each alkyl or aryl.

In Example 1, R, is methyl and R, is C,,-C,,,, with an average of C Thealdimines of ketimines of aminoguanidine, as illustrated by Examples 2and 3, have the following general structural formula:

OH R,

in which R, and R are each alkyl or aryl. In Example 2 R, is methyl andR is C -C with an average of C In Example 3, R, is methyl and R is C,,.

The aldimines of amides of aminoguanidine, as illustrated by Example 4,have the following general structural formula:

0 H NH in which R is aralkyl.

In Example 4, R is phenylstearyl.

The oxidation stability of a fuel in the form of gasoline, employing thenovel aminoguanidine compounds of the present invention, was tested bythe Induction Period Method, in accordance with ASTM Test D525. Theinhibitor agents .of the present invention, as set forth in Table I,below, were blended in a full boiling range catalytically crackedgasoline containing 3 cc. of uninhibited tetraethyl lead fluid pergallon within a -400 F. boiling range.

Utilizing the same base fuel as employed in Table 1, supra, therespective gasoline samples were subjected to a 5 hour accelerated gumtest. In this test, the gasoline also contained 3 cc. of tetraethyl leadfluid per gallon and, however, included 0.2 mg. copper naphthenate perliter, as a metal catalyst. The test results, comparing the uninhibitedgasoline and the same gasoline containing the additive compounds of theexamples, are set forth in the following Table II.

TABLE II Gum Conn. 02. mgll. lbs/1000 No copper Copper mg/ Compoundbbls. mg/IOO ml 100 ml.

Base gasoline 0 13.0 61.6 +Ex. l 10 8.5 41.0 +Ex. 2 10 3.4 4.0 +Ex. 3 103.5 3.3

The respective additives of the foregoing examples were next subjectedto a standard gasoline storage test. This test was used to determine thequantity of gum increase in both a gasoline blend comprising the samebase fuel as in Table l, supra, comprising 100 percent catalyticallycracked components and containing 3 cc. tetraethyl lead per gallonwithin a l0O-400 F. boiling range, and the same gasoline blendcontaining, also, the additive compositions of the examples. After beingmaintained at 110 F. for a period of 16 weeks, the amount of gumincrease was determined according to ASTM Test D381. The test resultscomparing the uninhibited gasolines and the same gasoline containing theadditive agents of the examples are set forth in Table Ill.

The oxidation and corrosion evaluation of the additive agents of thepresent invention with respect to lubricants, was next determined inaccordance with Federal Test Method 53-08. In this test the inhibitorswere blended in a base lubricant comprising the mixed caprylyl andpelargonyl esters of 2- methyl, 2-ethyl, 1,3-propanediol. The test wascarried out at a temperature of 400 F. for a period of 72 hours. Theresults of this test are shown in the following Table IV.

TABLE IV Weight loss of Compound copper Catalyst g Q q- Base lubricant 03.8 +Ex. l 01 L4 +Ex. 2 (H 03 +Ex. 4 03 0.5

From the foregoing comparative data, it will be apparent that the novelaminoguanidine compounds of the present invention are highly effectiveas antioxidants and metal deactivators for fuel oils and hydrocarbonlubricants. Although the present invention has been described withpreferred embodiments, it will be understood that various modificationsand adaptations thereof may be resorted to without departing from thespirit and scope of the invention and that the compositions thereindisclosed may also contain other additives intended to enhance theirproperties.

I claim:

1. An organic composition selected from the group consisting of liquidhydrocarbon fuels and hydrocarbon lubricants containing, in an amountsufficient to inhibit oxidation, an agent selected from the groupconsisting of ketimines of aminoguanidine, aldimines of ketimines ofaminoguanidine and aldimines of amides of aminoguanidine wherein saidketimines of aminoguanidine have the general structure:

Nil

01-1 NH R1 in which R, and R, are each alkyl or aryl; and the aldiminesof amides of aminoguanidine have the general structure:

in which R is aralkyl.

2. A composition as defined in claim 1 wherein said agent is present inan amount from about 0.1 to about 200 pounds per thousand barrels ofsaid composition.

3. A composition as defined in claim 1 wherein said agent is present inan amount from about 1 to about 10 pounds per thousand barrels of saidcomposition. 4. A composition as defined in claim 1 wherein saidcomposition is a liquid hydrocarbon comprising a petroleum distillatefuel having an initial boiling point from about 75 to about F. and anend boiling point from about 250 to about 750 F.

5. A composition as defined in claim 1 wherein said liquid hydrocarboncomprises a gasoline.

6. A composition as defined in claim 1 wherein said liquid hydrocarboncomprises a jet fuel.

7. A composition as defined in claim 1 wherein said liquid hydrocarboncomprises a diesel fuel.

8. A composition as defined in claim 1 wherein said compositioncomprises a lubricating oil.

9. A composition as defined in claim 1 wherein said liquid hydrocarboncomprises a turbine oil.

10. A composition as defined in claim 1 wherein said compositioncomprises a grease.

11. A composition as defined in claim 1 wherein said agent comprises themethyl coco ketimine of aminoguanidine having the structure shown inclaim 1 in which R, is methyl and R is coco.

12. A composition as defined in claim 1 wherein said agent comprises thesalicylaldimine of the methyl coco ketimine of aminoguanidine having thestructure shown in claim 1 in which R, is methyl and R is coco.

13. A composition as defined in claim 1 wherein said agent comprises thesalicylaldimine of the methyl nonyl ketimine of aminoguanidine havingthe structure shown in claim 1 in which R, is methyl and R is nonyl.

14. A composition as defined in claim 1 wherein said agent comprises thealdimine of the amide of aminoguanidine shown in claim 1 in which R isphenylstearyl.

2. A composition as defined in claim 1 wherein said agent is present inan amount from about 0.1 to about 200 pounds per thousand barrels ofsaid composition.
 3. A composition as defined in claim 1 wherein saidagent is present in an amount from about 1 to about 10 pounds perthousand barrels of said composition.
 4. A composition as defined inclaim 1 wherein said composition is a liquid hydrocarbon comprising apetroleum distillate fuel having an initial boiling point from about 75*to about 135* F. and an end boiling point from about 250* to about 750*F.
 5. A composition as defined in claim 1 wherein said liquidhydrocarbon comprises a gasoline.
 6. A composition as defined in claim 1wherein said liquid hydrocarbon comprises a jet fuel.
 7. A compositionas defined in claim 1 wherein said liquid hydrocarbon comprises a dieselfuel.
 8. A composition as defined in claim 1 wherein said compositioncomprises a lubricating oil.
 9. A composition as defined in claim 1wherein said liquid hydrocarbon comprises a turbine oil.
 10. Acomposition as defined in claim 1 wherein said composition comprises agrease.
 11. A composition as defined in claim 1 wherein said agentcomprises the methyl coco ketimine of aminoguanidine having thestructure shown in claim 1 in which R1 is methyl and R2 is coco.
 12. Acomposition as defined in claim 1 wherein said agent comprises thesalicylaldimine of the methyl coco ketimine of aminoguanidine having thestructure shown in claim 1 in which R1 is methyl and R2 is coco.
 13. Acomposition as defined in claim 1 wherein said agent comprises thesalicylaldimine of the methyl nonyl ketimine of aminoguanidine havingthe structure shown in claim 1 in which R1 is methyl and R2 is nonyl.14. A composition as defined in claim 1 wherein said agent comprises thealdimine of the amide of aminoguanidine shown in claim 1 in which R isphenylstearyl.